EP2229424A1 - Surface-modified conversion luminous substances - Google Patents

Surface-modified conversion luminous substances

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Publication number
EP2229424A1
EP2229424A1 EP08876948A EP08876948A EP2229424A1 EP 2229424 A1 EP2229424 A1 EP 2229424A1 EP 08876948 A EP08876948 A EP 08876948A EP 08876948 A EP08876948 A EP 08876948A EP 2229424 A1 EP2229424 A1 EP 2229424A1
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EP
European Patent Office
Prior art keywords
eu
characterized
ce
phosphor
si
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP08876948A
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German (de)
French (fr)
Other versions
EP2229424B1 (en
Inventor
Ralf Petry
Reinhold Rueger
Tim Vosgroene
Holger Winkler
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Merck Patent GmbH
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Merck Patent GmbH
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Priority to DE200710056342 priority Critical patent/DE102007056342A1/en
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Priority to PCT/EP2008/009142 priority patent/WO2010060437A1/en
Publication of EP2229424A1 publication Critical patent/EP2229424A1/en
Application granted granted Critical
Publication of EP2229424B1 publication Critical patent/EP2229424B1/en
Application status is Active legal-status Critical
Anticipated expiration legal-status Critical

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/0883Arsenides; Nitrides; Phosphides
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025Use of non-luminescent materials other than binders
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7715Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
    • C09K11/7721Aluminates; Silicates
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals comprising europium
    • C09K11/7734Aluminates; Silicates
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7774Aluminates; Silicates
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2933/00Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
    • H01L2933/0008Processes
    • H01L2933/0041Processes relating to wavelength conversion elements
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L33/00Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50Wavelength conversion elements
    • H01L33/501Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502Wavelength conversion materials

Abstract

The invention relates to surface-modified luminous particles based on luminescent particles containing at least one luminescent compound, with the exception of (Ca,Sr,Ba)2SiO4 or other silicates having one or more activator ions such as Eu, Ce, and Mn. At least one inorganic layer containing oxides/hydroxides of Si, Al, Zr, Zn, Ti and/or mixtures thereof, and an organic coating made of organosilanes or polyorganosiloxanes (silicones) and/or mixtures thereof, are applied to the luminescent particles. Also disclosed is a production method.

Description

Surface-modified conversion phosphors

The invention relates to surface-modified phosphor particles to which then an organic coating is applied a metal, transition metal or semimetal oxide coating as well as their

Manufacturing.

During the curing of the resin containing the LED phosphors, there is a sedimentation of the phosphor particles. As a result, creates an inhomogeneous and non-reproducible distribution of

Phosphors over the LED chip or in the remote phosphor layer. As a result, have the LEDs on large differences in light distribution; both the distribution to a LED is strongly dependent on the angle (Figure 1), as well as the properties of light from LED to LED within a batch is not uniform. Thereby, the LED manufacturer is forced to perform a complicated and expensive binning, which results in low yields of salable LEDs (The target bin with light properties which does meet the requirements, a yield of approximately up to 10% of total production. The remaining white LEDs are either destroyed, or as "open bin" often

Secondary brands for applications undemanding at low prices sold). This expense is clearly containing from price differences between blue and white LEDs phosphor LEDs, which may be up to 100%. The high initial cost of white LEDs in turn hinder the rapid substitution of inefficient and prone to short-life light bulbs, halogen lamps and fluorescent lamps with white LEDs.

Functionalization of phosphors is described in the literature. In A. Meijerink et al. , Phys. Chem. Chem. Phys., 2004, 6,

1633 - 1636 will be described how to nano-phosphors which have a reactive surface feature (intrinsic property of nanoparticles which have a large surface to volume ratio and high surface energy with bonds of any kind saturate) glycine as a linker to tetramethylrhodamine (dye) connects to observe charge transfer. However, the method described is unsuitable to phosphors to resins to bind or to achieve a Kompatibilisiereung.

From YT Nien et al. Materials Chemistry and Physics, 2005, 93, 79-83 is known how to embed nano-phosphors in HMDS (hexamethyldisilazane), to saturate the reactive and unstable surface. In this

Case will be no connection, but merely embedding of nano phosphor in a SiO 2 matrix.

From US 2007/0092758 a phosphor paste is known from a phosphor, a silane-containing dispersant and an organic

Resin. There are mixed phosphor, dispersant and binder and the phosphor dispersed in the binder. The dispersing agents used consist of a specific hydrophobic organic group, a hydrophobic group and a bound to the hydrophilic group silanol anchor group. For the homogeneous distribution of the phosphor, it is necessary in spite of the added dispersant, to subject the paste to grinding. This can lead to a deterioration of the properties of the phosphor, for example, by the high energy input or by contamination from the Mahlkörpermaterial.

The object of the present invention will now was the one hand, to avoid the abovementioned disadvantages as non-homogeneous and non-reproducible distribution of the phosphor particles over the LED chip and the other hand to provide a phosphor which can be incorporated into various binding systems simple. We have found now that this inhomogeneity of light distribution, which is caused by inhomogeneous phosphor layers is avoided by compatibilization of the phosphor surface with the silicone or epoxy resin. In the compatibilization of the surface of the phosphor is provided with functional chemical groups and linkers. These allow an adjustment of the phosphor particles to the hydrophilic or hydrophobic properties of the resin. Characterized homogeneous mixtures of resin and phosphor can be produced which do not tend to flocculate.

Accordingly, the present invention provides surface-modified phosphor particles on the basis of luminescent particles containing a luminescent compound is at least, with (Ca, Sr, Ba) 2 SiO 4 and other silicates with one or more

Activator ions such as Eu, Ce and Mn and / or Codotanten are excluded based on Fe, Cu and / or Zn, and wherein the luminescent particles are at least one inorganic layer containing oxides / hydroxides of Si, Al, Zr, Zn, Ti and / or mixtures thereof, and then an organic coating comprising organosilanes or

Polyorganosiloxanes (silicones) and / or mixtures thereof is applied.

Preferably, the luminescent particles comprise at least one of the following compounds:

(Y, Gd, Lu, Sc, Sm, Tb) 3 (Al, Ga) 5 O 2 -Ce (with or without Pr), YSiO 2 N: Ce, Y 2 Si 3 O 3 N 4 ICe, Gd 2 Si 3 O 3 N 4 ICe, (Y, Gd, Tb, Lu) 3 Al 5-x Si x Oi 2 -χN x: Ce, BaMgAI 10 Oi 7: Eu (with or without Mn), SrAI 2 O 4: Eu , Sr 4 AII 4 O 25: Eu, (Ca, Sr, Ba) Si 2 N 2 O 2: Eu, SrSiAI 2 O 3 N 2: Eu, (Ca, Sr, Ba) 2 Si 5 N 8: Eu, (Ca , Sr, Ba) SiN 2: Eu, CaAISiN 3: Eu, molybdates, tungstates, vanadates,

Group III-nitrides, oxides, individually or mixtures thereof with one or more activator ions such as Ce, Eu, Mn, Cr, Tb and / or Bi, - A -

wherein the above limitation with respect to the doped / co-doped silicates still applies.

The functional groups on the surface of the phosphor form an entanglement and / or crosslinking or chemical compound with the components of the resin. In this way can a homogenous

fix distribution of the phosphor particles in the resin. During Harzaushärtungsprozesses no sedimentation of the phosphor particles occurs. enacting particular for wet-chemically produced, a high homogeneity of the particle properties (eg morphology, particle size distribution) phosphors can be inventively advantageous phosphor layers realized.

The light properties of a white LED, which are provided with the inventively coated phosphors of Figure 1 (black curve) can be taken: the CCT is homogeneous over the entire angular range over the LED; ie the observer takes in any position the same color temperature ( "light color") is true. On the contrary, shows (via mix & fire produced) phosphors with conventional fitted, white LED a large variance of the CCT, so that the observer one in different directions perceives other light color.

In the functionalization or surface modification reactive hydroxy groups are formed on the surface of the phosphor particles by a metal, transition metal or metalloid oxide on wet chemical or vapor deposition processes (CVD) process first.

The inorganic coating contains preferably nanoparticles and / or layers of oxides / hydroxides of Si, Al, Zr, Zn, Ti and / or mixtures thereof. Particularly preferred is a silica / -hydroxid-

Coating because it has a particularly large reactive hydroxyl groups, whereby a further addition of an organic coating is facilitated.

The inorganic coating of oxides / hydroxides of AI, Zr, Zn, Ti and / or mixtures thereof, is preferably substantially transparent, that is, they must both for the excitation as well as for the emission spectrum of conversion phosphors used in each case a 90% to 100% ensure transparency owned. On the other hand, the transparency of the coating according to the invention for all wavelengths that are not the excitation and emission wavelengths correspond to less than 90% to 100% may be.

The coated phosphor particles are then coated with an organic, preferably substantially transparent coating comprising organosilanes or polyorganosiloxanes (silicones) and / or mixtures thereof, provided. This coating is also wet-chemically or by a

Evaporation process. The silicon-organic compounds react with the surface OH groups of the phosphor particles or the inorganic coating. The chains of the organic silicon compound form a more or less porous layer to the phosphor particles. By modifying the organic chains of the

Silicon compounds, the desired hydrophobicity of the phosphor particles, structure of the oligomer / polymer chains and the coupling of (physical and / or chemical) to the resin is controlled. As organosilanes alkoxysilanes are preferably used. Examples of organosilanes sfnd propyltrimethoxysilane, propyltriethoxysilane,

Isobutyltrimethoxysilane, n-octyltrimethoxysilane, i-octyltrimethoxysilane, n- octyltriethoxysilane, n-decyltrimethoxysilane, dodecyltrimethoxysilane, hexadecyltrimethoxysilane, vinyltrimethoxysilane, preferably n- octyltrimethoxysilane and n-octyltriethoxysilane. Suitable oligomeric, alcohol-free organosilane is inter alia suitable under the

Trade name "Dynasylan ®" marketed by the company. Sivento products, such. As Dynasylan HS 2926, Dynasylan HS 2909, Dynasylan HS2907, Dynasylan HS 2781, Dynasylan HS 2776, Dynasylan HS 2627. In addition, oligomeric vinylsilane and aminosilane is as the organic coating. Functionalized organosilanes are, for example, 3-aminopropyltrimethoxysilane, 3-methacryloxytrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, beta- (3,4-

are epoxycyclohexyl) ethyltrimethoxysilane, gamma-lsocyanatopropyltri- methoxysilane, 1, 3-bis (3-glycidoxypropyl) -1, 1, 3.3, tetramethyldisiloxane, ureidopropyltriethoxysilane, preferably 3-aminopropyltrimethoxysilane, 3-methacryloxytrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, beta- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-lsocyanatopropyltri- trimethoxysilane.

The following compounds are particularly preferably used alone or in mixtures:

• Silquest A-186 ® [beta- (3,4-epoxycyclohexyl) ethyltrimethoxysilane] • Silquest A-1310 ® gamma isocyanatopropyltriethoxysilane

• Silquest A-1110 ® gamma-aminopropyltrimethoxysilane

• Silquest A-1524 ® gamma Harnstoffpropyltrimethoxysilan

• Silquest A-174 ® gamma-methacryloxypropyltrimethoxysilane

• Silquest A-151 ® vinyltriethoxysilane

Examples of polymeric silane or polyorganosiloxanes are described in WO 98/13426 and z. B. from the company. Sivento sold under the trademark Hydrosil ®.

The choice of a suitable silane depends among other things on whether the

should be sent to an epoxy resin or a silicone resin binding the silane. one will use an Langzeitstrahlungs- and thermally stable silicone resin for high-performance LEDs (high-power LEDs with the electrical connection performance of min. 1 W), for low- or medium-power LEDs (electrical connection power <1W) on the other hand, as described for example for Backlighting- applications are suitable, you will choose a less extreme temperatures and radiation stable epoxy resin.

The particle size of the phosphors according to the invention is between 1 and 40 microns, preferably between 2 microns and 20 microns.

The thickness of the coating of the invention, consisting of inorganic and organic coating is between 5 nm and 200 nm, preferably 10 nm and 50 nm. The particle size of the primary particles of the metal, transition metal or Halbmetalloxid-

Coating is between 5 nm and 50 nm. The coating of the invention is not necessarily homogeneous, but may also be in the form of islands or in the form of drops on the surface of the particles. The organic coating thickness depends on the molecular weight of the organic groups and can be between 0.5 nm and 50 nm, preferably between 1 and 5 nm.

The amount of organic coating is from 0.02 to 5 wt.% Based on the surface-coated phosphor particles by weight, preferably 0.1 to 2.%.

Another object of the present invention is characterized by the steps of a method for producing a surface-modified phosphor particles:

a. Producing a phosphor particle by mixing at least two starting materials and at least one dopant and thermal treatment at a temperature T> 150 0 C,

b. of the phosphor particles is containing in a wet chemical or vapor deposition with an inorganic layer

Oxides / hydroxides of AI, Zr, Zn, Ti and / or mixtures thereof, coated, c. Applying an organic coating comprising organosilanes or polyorganosiloxanes (silicones) and / or mixtures thereof.

The coating of the phosphor particles is particularly preferably wet-chemically by precipitation of the above mentioned oxides or hydroxides in aqueous dispersion. For this purpose, the uncoated phosphor is suspended in a reactor in water and by simultaneous metered addition of at least one metal salt and at least one precipitating agent under

coated stir with the metal oxide or hydroxide. As an alternative to metal salts, organometallic compounds such as metal alkoxides, can be metered, which then form by hydrolytic decomposition of metal oxides or hydroxides. Another possible way to coat the particles, the coating is a sol-gel

Process in an organic solvent such as ethanol or methanol. This method is particularly suitable for water-sensitive materials and for acid- or alkali-sensitive materials.

The starting materials for producing the phosphor consist, as mentioned above, from the base material (for. Example salt solutions of aluminum, yttrium and cerium), and at least one dopant, preferably europium or cerium and optionally further Gd, Lu, Sc, Sm containing materials, Tb, Pr and / or Ga -. As starting materials, inorganic and / or organic substances such as nitrates, carbonates, bicarbonates, phosphates, carboxylates, alcoholates, acetates, oxalates, halides, sulfates, organometallic compounds, hydroxides and / or oxides of the metals, semi-metals, transition metals and / or rare earths are suitable which are dissolved in inorganic and / or organic liquids and / or suspended. Preferably mixed nitrate solutions, chloride or hydroxide are used which comprise the corresponding elements in the required stoichiometric ratio.

The wet-chemical preparation has over the conventional

Solid-state diffusion method (English, mixing and firing) in general, that the resulting materials have the advantage of a greater uniformity with respect to the stoichiometric composition, the particle size and morphology of the particles from which the phosphor according to the invention is prepared.

consisting for example of a mixture of yttrium nitrate, cerium nitrate and Aluminiumnitrat- following known methods are preferred for the wet-chemical production of a phosphor particle:

• co-precipitation with an NH 4 HCO 3 solution (see, eg, Jander, Blasius

Textbook of analyte. u. prep. anorg. Chem. 2002)

• Pecchini method with a solution of citric acid and ethylene glycol (see, eg, Annual Review of Materials Research Vol. 36: 2006, 281-331)

• combustion process using urea

• spray drying of aqueous or organic salt solutions (starting materials)

• spray pyrolysis (also called spray pyrolysis) aqueous or organic salt solutions (starting materials)

In the above-mentioned co-precipitation according to the invention particularly preferred example chloride or nitrate solutions of the corresponding phosphor treated with a NH 4 HCθ 3 solution, thereby forming the phosphor precursor. In the Pecchini method, the above-mentioned nitrate solutions of the corresponding phosphor, for example, treated at room temperature with a precipitating agent consisting of citric acid and ethylene glycol and then heated. Increasing the viscosity results in phosphor formation.

In the known combustion methods, the above-mentioned nitrate solutions of the corresponding phosphor, for example, dissolved in water, then boiled under reflux and treated with urea, whereby the phosphor precursor slowly.

Spray pyrolysis is one of the aerosol method, by atomization of solutions, suspensions or dispersions in a heated in various ways reaction chamber (reactor) and the formation and deposition of solid particles are characterized. In contrast to spray drying with hot gas temperatures <200 0 C found in the spray pyrolysis as a high-temperature process in addition to the

Evaporation of the solvent in addition, the thermal decomposition of the starting materials used (eg., Salts), as well as the formation of new materials (eg., Oxides, mixed oxides) instead.

The above-mentioned 5 process variants are described in detail in DE 102006027133.5 (Merck) describes the full extent in the context of the present

Application is incorporated by reference.

The production of surface-modified phosphor particles according to the invention can be prepared by various wet-chemical methods by

1) homogeneously precipitating the ingredients, followed by separation of the solvent and a single- or multi-stage thermal post-treatment, can being carried out, a step in a reducing atmosphere, 2) the mixture is finely divided, for example by means of a spray process, and a distance of the solvent is carried out, followed by a single- or multistep thermal after-treatment can be carried out with a step in a reducing atmosphere, or

3) the mixture is finely divided, for example, with the aid of a spray process, and removing the solvent along with a pyrolysis followed by a single- or multi-stage thermal post-treatment, wherein one of these steps can be carried out in a reducing atmosphere.

4) with the aid of methods 1 - 3 manufactured phosphors are coated subsequently wet-chemically.

Preferably, the wet chemical preparation of the phosphor by the precipitation and / or sol-gel process occurs.

In the above-mentioned thermal aftertreatment, it is preferred if the annealing is at least partially under reducing conditions

is performed (for example, with carbon monoxide, forming gas, pure hydrogen, mixtures of hydrogen with an inert gas or at least a vacuum or oxygen-deficient atmosphere).

Generally, it is also possible to uncoated the invention

Phosphors on the solid-state diffusion method to produce, but this causes the disadvantages already mentioned.

In a further embodiment, it may also be advantageous according to the invention, when omitting the coating with an inorganic oxide and the phosphor particles provides only with an organic coating. Using the above procedures any desired external shapes of the phosphor particles can be produced as spherical particles, flakes and structured materials and ceramics.

The excitability of the phosphors according to the invention also extends over a wide range varying from about 250 nm to 560 nm, preferably 380 nm to about 500 nm is sufficient. These phosphors for excitation by UV and blue-emitting primary light sources such as LEDs or conventional discharge lamps are suitable (for example based on Hg).

Another object of the present invention is a. Lighting unit having at least one primary light source whose emission maximum in the range, preferably 250 nm to 530 nm 380 nm to about 500 nm, where the primary radiation is converted partially or totally by the novel surface-modified phosphors into longer-wave radiation. Preferably, this illumination unit emits white light or emits light having a certain color point (color-on-demand principle).

In a preferred embodiment of the illumination unit of the invention is the light source is a luminescent indium aluminum gallium nitride, in particular of the formula Iniga j Al k N, where 0 <i, 0 <j, 0 <k, and i + j + k = 1.

The skilled worker is aware of possible forms of such light sources. This may be light-emitting LED chips having various structures.

In a further preferred embodiment of the invention

Lighting unit is the light source is a luminescent on ZnO, TCO (transparent conducting oxide), ZnSe or SiC-based arrangement or also a rating based on an organic light-emitting layer arrangement (OLED).

In a further preferred embodiment of the invention

Lighting unit is the light source is a source which shows the electroluminescence and / or photoluminescence. It may be the light source and to a plasma or discharge source.

The phosphors according to the invention can either be dispersed in a resin (for example epoxy or silicone resin) to be arranged directly on the primary light source, or disposed away from this, depending on the application (the latter arrangement also includes "remote phosphor technology" a). the advantages of "remote phosphor technology" are well known in the art and can be seen as the following publication: Japanese Journ. of Appl. Phys. Vol. 44, No. 21 (2005). L649- L651.

In a further embodiment it is preferable if the optical

Coupling of the illumination unit between the coated phosphor and the primary light source is implemented by a light-conducting arrangement. Thereby, it is possible that the primary light source is installed at a central location and to be optically coupled to the phosphor by means of light-conducting devices, such as light-conducting fibers. In this manner, the illumination can be adjusted wishes lamps merely consisting of one or different phosphors, which may be arranged to form a phosphor screen, and a light guide which is coupled to the primary light source realized. In this way it is possible to place a strong primary light source to a low for the electrical installation place and without installing additional electrical cabling, but only by laying of optical fibers at any location lights of phosphors, which are coupled to the optical fibers.

Another object of the present invention is the use of the phosphors according to the invention for partial or complete conversion of the blue or near-UV emission from a luminescent diode in.

Another object of the present invention is the use of the phosphors according to the invention in electroluminescent materials, such as electroluminescent films (also lighting films or light films) in which, for example, zinc sulfide or zinc sulfide doped with Mn 2+, Cu +, or Ag + as an emitter is used, emitting in the yellow green region. The applications of the

Electroluminescent film are, for example, advertising, display backlight in liquid crystal displays (LCDs), and thin film transistor display (TFT) displays, self-illuminating vehicle license plates, floor graphics (in conjunction with a crush-resistant and slip-resistant laminate), in display and / or control elements for example, in automobiles, trains, ships and aircraft, or also domestic appliances, garden, measuring or sports and leisure equipment.

The following examples illustrate the present invention. However, they are not to be regarded as limiting. All compounds or components which can be used in the preparations are either known and commercially available or can be synthesized by known methods. The temperatures indicated in the examples are always in 0 C. It furthermore goes without saying that the added amounts of the components always add up both in the description and in the examples in the compositions to 100%. Percentage data given should always be regarded in the given context. Always usually refer but to the weight of the part or total.

Examples

Embodiment 1: coating a YAG: Ce phosphor powder with SiO 2 (generating active hydroxy groups)

50 g of a YAG: Ce phosphor are suspended in a 2-L reactor equipped with ground-glass lid, heating mantle and reflux condenser in 1 liter of ethanol. A solution of 17 g of ammonia water is added (25 wt% NH 3) in 170 g of water. While stirring, a solution of 48 g of tetraethylorthosilicate (TEOS) in 48 g of anhydrous ethanol is slowly added dropwise (about 1 ml / min) at 65 0 C. After completion of the addition the suspension is stirred at 2 hours, brought to room temperature and filtered. The residue is washed with ethanol and dried.

Exemplary Embodiment 2: coating a YAG: Ce phosphor having Al 2 O 3

In a glass reactor with a heating jacket 50 g of YAG: Ce phosphor in

suspended 950 g of demineralized water. To the suspension an aqueous solution of 98.7 g of AlCl 3 .6H 2 O per Kg of solution are under stirring at 80 0 C 600g, Λ A metered hours in Fig.2. Here, the pH by addition of sodium hydroxide solution is kept constant at 6.5. After the end of the metered addition for 1 hour, stirring is continued at 80 0 C, then at

Cooled to room temperature, filtered off the phosphor, washed with water and dried. Embodiment 3 Coating of a nitride phosphor powder with SiO 2

50 g Sr o, 5 Bao, 5 SiN 2: Eu, in a 2-L reactor equipped with ground-glass lid,

Heating mantle, and reflux condenser in 1 liter of ethanol suspended. A solution of 17 g of ammonia water is added (25 wt% NH 3) in 170 g of water. While stirring, a solution of 35 g of tetraethylorthosilicate (TEOS) in 35 g of anhydrous ethanol is slowly added dropwise (about 1 ml / min) at 65 0 C. After completion of the addition the suspension is stirred at 2 hours, brought to room temperature and filtered. The residue is washed with ethanol and dried.

Embodiment 4: coating a nitride phosphor powder with AI 2 O 3

In a glass reactor with a heating jacket 50 g (015 Ca Sr 01S) are 2 Si 5 N 8) Eu suspended in 950 g of demineralized water. To the suspension an aqueous solution of 76.7 g of AlCl 3 .6H 2 O per Kg of solution are under stirring at 80 0 C 600g, metered in over 2 Vi hours. Here, the pH by addition of sodium hydroxide solution is kept constant at 6.5. After the end of metering in a further 1 hour is stirred at 8O 0 C, then is cooled to room temperature, the phosphor is filtered off, washed with water and dried.

Coating of the phosphor of Examples 1 to 4, with functional groups: Working Example 5a: silanes for Epoxypotymere (Hydrophilic variant, GE-silanes, epoxy-silane, suitable for epoxy resins)

100 g of a phosphor described in the above examples, coated with SiO 2 and / or Al 2 O 3 are suspended in 1350 ml demineralized water with vigorous stirring. The pH of the suspension is adjusted with 5 wt% H 2 SO 4 to pH = 6.5 and the suspension heated to 75 ° C. Subsequently, 4.0 g of a 1: 1 mixture of Silquest A-186 ® [beta- (3,4-epoxycyclohexyl) ethyltrimethoxysilane], and Silquest A-1310 ® [Gamma-isocyanatopropyltriethoxysilane] within 60 min with moderate agitation to suspension were metered. After the addition is then stirred for 15 minutes to complete the coupling of the silanes to the surface. The pH value is% H 2 SO 4 corrected by means of 5 to 6.5. The suspension is then filtered and washed with deionised water until salt-free. Drying is carried out for 20 h at 130 0 C. The phosphor powder thus obtained is then sieved through 20 micron sieve.

Working Example 5b: silanes especially for silicone-phosphor

coupling

100 g of a phosphor described in the above examples, coated with SiO 2 and / or Al 2 O 3 are suspended in 1350 ml demineralized water with vigorous stirring. The pH of the suspension is washed with 5 wt

% H 2 SO 4 adjusted to pH = 6.5 and the suspension heated to 75 0 C. Subsequently, 6.0 g of a 1 are: 2 mixture of Silquest ® A-1110 [gamma aminopropytrimethoxysilan] and Silquest A-1524 ® [gamma Harnstoffpropyltrimethoxysilan] were metered in within 75 min with moderate stirring to the suspension. After the addition is then stirred for 15 minutes to complete the coupling of the silanes to the surface. The pH value is% H 2 SO 4 corrected by means of 5 to 6.5.

The suspension is then filtered and washed with deionised water until salt-free. Drying is carried out for 20 hours at 14O 0 C. The phosphor powder thus obtained is then sieved through 20 micron sieve.

Working Example 5c: vinyl silane for silicone coupling fluorescent

100 g of a described in the above examples, with SiO 2 and / or

Al 2 O 3 coated phosphor are suspended in 1350 ml demineralized water with vigorous stirring. The pH of the suspension is adjusted with 5 wt% H 2 SO 4 to pH = 6.8 and the suspension heated to 75 ° C. 2 mixture of Silquest ® A-174 [Gamma-methacryloxypropyltrimethoxysilane] and Silquest A-151 ®: Next, 6.0 g of a 1 are

[Vinyltriethoxysilane] were metered in within 90 min with moderate stirring to the suspension. After the addition is then stirred for 15 minutes to complete the coupling of the silanes to the surface. The pH value is% H 2 SO 4 corrected by means of 5 to 6.5. The suspension is then filtered and washed with deionised water until salt-free. Drying is carried out for 20 h at 140 0 C. The phosphor powder thus obtained is then sieved through 20 micron sieve.

Working Example 6 Preparation of a LED

There are the following mixtures in a Speed ​​Mixer ® (speed 3000 rpm, time: 5 min, room temperature) were prepared: 50 ml of the two resin components JCR 6122 a and b are mixed with 8% from that of Example 3, a, b, or. c compatibilized phosphor powder and 1, 2% of silica powder having an average

Diameter of 0.5 micron mixed. The two resin mixtures are combined, stirred and degassed. Thereafter, 10 ml are filled into the reservoir of a Jetdispensers or Schraubendosierventildispensers. Under the dispensing valve bonded COB (chip on board) crude LED packages are placed. Then are added dropwise to the Dispender glob tops of the resin mixture to the chips of the crude LED packages. These coated LEDs are heated in an oven at 150 0 C for 1 hour. Here, the resin hardens.

DESCRIPTION OF THE FIGURES

In the following the invention will be explained in detail with reference to several embodiments. Show it:

Fig. 1: Uncoated phosphors (1) in resin (3) incorporated over the LED chip (2). The left graph shows the state directly after the application of the phosphor resin mixture to the chip represents After curing of the resin (4) is the state of the phosphor resin mixture (right drawing) as follows:. The larger phosphor particles have a strong tendency to sedimentation. Thus, the particles are distributed inhomogeneous. This distribution is "frozen" after the resin hardening.

Fiq.2: According to the invention coated phosphors (1) in resin (3) incorporated over the LED chip (2). The left figure shows the homogeneous distribution of the uniform phosphor powder. This homogeneity is made possible through the inventive compatibilizing the phosphor surface with the resin properties. During curing there will be no disruption of distribution, because the

Phosphors are inventively crosslinked with the resin or chemically bonded. Finally, the phosphor layer over the LED is uniform (see right diagram).

Fig. 3: shows silicone or silane coated phosphor particles (1) with two different structures with respect to the polymer chains (2).. The surface-bound polymer chains improve the one hand, the dispersibility of the phosphor particles in the resin. On the other hand, the polymer chains may act as "spacer", thus preventing the agglomeration of phosphor particles. Furthermore, a connection of the compatibilized phosphor particles to the resin (cross-linking or

obtained reaction with constituents of the resin).

Claims

claims
1. Surface-modified phosphor particles on the basis of luminescent particles containing a luminescent compound at least, in which (Ca 1 Sr 1 Ba) 2 SiO 4 and other silicates with one or more activator ions such as Eu, Ce and Mn and / or Codotanten based on Fe , Cu and / or Zn except as luminescent compounds, characterized in that the luminescent particles is at least an inorganic layer, comprising oxides / hydroxides of Si, Al, Zr, Zn, Ti and / or mixtures thereof, and an organic coating organosilanes or polyorganosiloxanes (silicones) and / or mixtures thereof is applied.
2. The surface-modified phosphor particles according to claim 1, characterized in that the luminescent particles is at least one luminescent compound selected from the group of (Y, Gd, Lu, Sc, Sm, Tb) 3 (Al, Ga) 5 O 12-1 Ce (with or without Pr), YSiO 2 N: Ce,
Y 2 Si 3 O 3 N 4) Ce, Gd 2 Si 3 O 3 N 4 ICe, (Y 1 Gd 1 Tb 1 Lu) 3 Al 5 - X Si X O 12-X N x ICe, BaMgAli 0 Oi 7: Eu (with or without Mn), SrAI 2 O 4: (Eu: Eu, Sr 4 Ali 4 O 25: Eu, (Ca, Sr, Ba) Si 2 N 2 O 2: Eu, SrSiAI 2 O 3 N 2 Ca, Sr, Ba) 2 Si 5 N 8: Eu, (Ca, Sr, Ba) SiN 2: Eu, CaAISiN 3: Eu, molybdates, tungstates, vanadates, group III-nitrides, oxides, individually or mixtures thereof contain one or more activator ions such as Ce, Eu, Mn, Cr, Tb and / or Bi.
3. The surface-modified phosphor particles according to claim 1 and / or 2, characterized in that the particle size of the
Phosphor particles between 1 and 40 microns.
4. The surface-modified phosphor particles according to one or more of claims 1 to 3, characterized in that the inorganic coating and the organic coating are substantially transparent.
5. A method for producing a surface-modified phosphor particle according to claim 1, characterized by the steps of:
a) preparing a phosphor particle by mixing at least two starting materials and at least one dopant and thermal treatment at a temperature T> 150 C 0 1
b) the phosphor particles containing thereof, coated oxides / hydroxides of AI, Zr, Zn, Ti and / or mixtures in a wet chemical or vapor deposition with an inorganic layer,
c) applying an organic coating from
Organosilanes or polyorganosiloxanes (silicones) and / or mixtures thereof.
6. The method according to claim 5, characterized in that the inorganic oxide and the organic coating are substantially transparent.
7. The method according to claim 5 and / or 6, characterized in that the phosphor is wet chemically prepared from organic and / or inorganic metal, semimetal, transition metal and / or rare-earth salts by means of sol-gel process and / or precipitation ,
8. The method according to one or more of claims 5 to 7, characterized in that the coating is carried out with at least one inorganic oxide by addition of aqueous or non-aqueous solutions of non-volatile salts and / or organometallic compounds.
9. The method according to one or more of claims 5 to 8, characterized in that the starting materials and the dopant inorganic and / or organic substances such as nitrates, carbonates, bicarbonates, phosphates, carboxylates, alcoholates, acetates, oxalates, halides, sulfates, organometallic compounds, hydroxides and / or oxides of the metals, semi-metals, transition metals and / or rare earths, which are dissolved in inorganic and / or organic liquids and / or suspended.
10. The method according to one or more of claims 5 to 9, characterized in that the phosphor particles consist of at least one of the following fluorescent materials:
(Y, Gd, Lu, Sc, Sm, Tb, Th 1 Ir, Sb, Bi) 3 (Al, Ga) 5 O 12: Ce (with or without Pr), YSiO 2 N: Ce, Y 2 Si 3 O 3 N 4: Ce, Gd 2 Si 3 O 3 N 4: Ce, (Y 1 Gd 1 Tb 1 Lu) 3 Al 5-x Si x Oi 2-x N x: Ce, BaMgAli Oi 0 7: Eu (with or without Mn), SrAI 2 O 4: Eu, Sr 4 Al 14 O 25: Eu, (Ca, Sr, Ba) Si 2 N 2 O 2: Eu, SrSiAI 2 O 3 N 2: Eu,
(Ca, Sr, Ba) 2 Si 5 N 8: Eu, (Ca, Sr, Ba) SiN 2: Eu, CaAISiN 3: Eu, molybdates, tungstates, vanadates, Group III-nitrides, oxides, individually or mixtures thereof with one or more activator ions such as Ce, Eu, Mn, Cr, Tb and / or Bi, in which (Ca 1 Ba 1 Sr) 2 SiO 4 and other silicates with one or more activator ions such as Eu, Ce or Mn and / or
Codotanten are based on Fe, Cu and / or Zn excluded.
11. The method according to claim 5, characterized, in that
Process step b), namely the coating with an inorganic layer, is eliminated.
12. A lighting unit comprising at least one primary light source whose emission maximum is in the range 250 nm to 530 nm, preferably between 380 nm and 500 nm, this radiation being converted partially or completely into longer-wave radiation by surface-modified phosphor particles according to one or more of claims 1 to 6 ,
13. Lighting unit according to claim 12, characterized in that it is luminescent in the light source is a
Indium aluminum gallium nitride, in particular of the formula lniGa j Al k N, where 0 <i, 0 <j, 0 <k, and i + j + k = 1 is.
14. The illumination unit according to claim 12, characterized in that the phosphor is remotely located directly on the primary light source and / or from this.
15. Lighting unit according to claim 12, characterized in that the optical coupling between the phosphor and the primary light source is implemented by a light-conducting arrangement.
16. Lighting unit according to claim 12, characterized in that it is at the light source is a material based on an organic light-emitting layer material.
17. Lighting unit according to claim 12, characterized in that it is at the light source is a source which shows the electroluminescence and / or photoluminescence.
18. Use of at least one surface-modified
Phosphor particles according to claim 1 as conversion phosphor for conversion of the primary radiation into a certain color point by the color-on-demand concept.
19. Use of at least one surface-modified
Phosphor particles according to claim 1 for the conversion of the blue or near-UV emission into visible white radiation.
EP08876948.4A 2007-11-22 2008-10-29 Surface-modified conversion luminous substances Active EP2229424B1 (en)

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PCT/EP2008/009142 WO2010060437A1 (en) 2007-11-22 2008-10-29 Surface-modified conversion luminous substances

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